Mechanochemical\nDecarbonylative Cross-Coupling of\nAmides via Cooperative Catalysis and Triple C–N/C–C/C–H\nActivation

Mechanochemical solvent-less cross-couplings have emerged\nas a\npowerful frontier in the formation of carbon–carbon and carbon–heteroatom\nbonds under sustainable conditions. However, despite considerable\nprogress, mechanochemical decarbonylative cross-couplings have been\nunexplored. Herein, we report the first decarbonylative mechanochemical\ncross-coupling for the heteroarylation of amides by a triple C–N/C–C/C–H\nactivation. The catalytic system exploits cooperative Ni/Cu catalysis\nto simultaneously activate the amide N–C(O) and the heterocycle\nC–H bonds, resulting in a highly chemoselective coupling. The\nreaction is characterized by a broad scope of the amide and the heterocyclic\ncomponent to furnish heterobiaryls, which are among the most privileged\nscaffolds in organic synthesis. We demonstrate that decarbonylative\nmechanochemical cross-couplings will provide novel access to a range\nof valuable products that are among the most common structures in\norganic chemistry.